Air-Stable and Reusable Cobalt Phosphide Nanoalloy Catalyst for Selective Hydrogenation of Furfural Derivatives

While metal phosphides have begun to attract attention as electrocatalysts, they remain underutilized in the field of liquid-phase molecular transformations. Herein, we describe a supported cobalt phosphide nanoalloy (nano-Co₂P) that functions as a highly efficient, reusable heterogeneous catalyst for the selective hydrogenation of furfural derivatives. The carbonyl moieties of several furfural derivatives were selectively hydrogenated to produce the desired products in high yields. In contrast to conventional nonprecious metal catalysts, nano-Co₂P uniquely exhibited air stability, which enabled easy and safe handling and precluded the need for H₂ pretreatment. Infrared and density functional theory studies revealed that the highly efficient hydrogenation is due to the favorable activation of the carbonyl moiety of furfural derivatives through the backdonation to its π* orbital from the Co d-electrons.Hiroya Ishikawa, Min Sheng, Ayako Nakata, Kiyotaka Nakajima, Seiji Yamazoe, Jun Yamasaki, Sho Yamaguchi, Tomoo Mizugaki, and Takato Mitsudome. Air-Stable and Reusable Cobalt Phosphide Nanoalloy Catalyst for Selective Hydrogenation of Furfural Derivatives. ACS Catalysis 2021, 11, 750-757, DOI: 10.1021/acscatal.0c03300.This document is the unedited Author’s version of a Submitted Work that was subsequently accepted for publication in ACS Catalysis, copyright © American Chemical Society after peer review. To access the final edited and published work see https://doi.org/10.1021/acscatal.0c03300

Diagnosing nocturnal frontal lobe epilepsy: A case study of two children

AbstractWe describe two children of nocturnal frontal lobe epilepsy (NFLE) diagnosed using carefully observed nocturnal sleep EEGs and detailed patient histories.Case #1, a 14-year-old boy, showed repeated generalized tonic convulsions and frequent eyes opening seizures during sleep. Conventional EEGs – done with the patient awake or in sleep stage I – showed no abnormalities, while a nocturnal sleep EEG – done during in sleep stage II – revealed the repeated, sharp wave bursts predominantly in the right frontal lobe characteristic of NFLE. During these wave bursts, we noticed the boy's eyes opening, although his parents had not been aware this NFLE symptom.Case #2, a 12-year-old boy, showed one daytime generalized convulsion. He had also been suffering from repeated paroxysmal episodes similar to parasomnia – waking up, sitting, walking, screaming, and speaking – which always followed the same patterns lasting several minutes. During the nocturnal sleep EEG, episodes occurred twice, showing abnormal epileptic discharges predominantly in the frontal lobe. His parents did not mention the episodes to us until questioned, as they had recognized them as parasomnia. The previous conventional EEG showed abnormal slow waves in the frontal lobe, which led us to suspect frontal lobe epilepsy and to take a detailed patient history.The frequency and stereotypy of their symptoms during sleep caused us to perform nocturnal sleep EEGs and led us NFLE diagnosis. Detailed patient histories including sleep habits and carefully observed nocturnal sleep EEGs enabled us to recognize these NFLE clinical features

2-Diphenylphosphanyl-4-pyridyl(dimethyl) amine as an effective ligand for the ruthenium(II) complex catalyzed homogeneous hydration of nitriles under neutral conditions

New homogeneous catalyst comprised of [Ru(methallyl)(2)(cod)] (cod = 1,5-cyclooctadiene) (1) and 2-diphenylphosphanyl-4-pyridyl(dimethyl) amine (2) is shown to efficiently catalyze the hydration of various nitriles under neutral conditions. The hydration proceeds in the presence of 0.5 mol% of the ruthenium catalyst at 80 degrees C in 1,2-dimethoxyethane solution and the corresponding amide is obtained within few hours without the formation of by products. Comparison of some phosphine ligands for the hydration reveals that the dimethylamino moiety of 2 improves the catalytic performance dramatically

Wacker-oxidation of Ethylene over Pillared Layered Material Catalysts

This paper concerns the Wacker oxidation of ethylene by oxygen in the presence of water over supported Pd/VOx catalysts. High surface area porous supports were obtained from layer-structured materials, such as, montmorillonite (MT), laponite (LT) (smectites), and hydrotalcite (layered double hydroxide, LDH) by pillaring. Before introduction of Pd, supports MT and LDH were pillared by vanadia. The laponite was used in titania-pillared form (TiO2-LAP) as support of Pd/VOx active component. Acetaldehyde (AcH), acetic acid (AcOH) and CO2 were the products with yields and selectivities, depending on the reaction conditions and the properties of the applied catalyst. Under comparable conditions the pillared smectite catalysts gave higher AcH yield than the pillared LDH catalyst. UV vis spectroscopic examination suggested that the pillared smectites contained polymeric chains of VO4, whereas only isolated monomeric VO4 species were present in the pillared LDH. The higher catalytic activity in the Wacker oxidation was attributed to the more favorable redox property of the polymeric than of the monomeric vanadia. The V3+ ions in the polymeric species can reduce O2 to O2- ions, whereas the obtained V5+ ions are ready to pass over O to Pd0 to generate PdO whereon the oxidation of the ethylene proceeds

Gold-catalyzed conversion of lignin to low molecular weight aromatics

A heterogeneous catalyst system, employing Au nanoparticles (NPs) and Li-Al (1:2) layered double hydroxide (LDH) as support, showed excellent activity in aerobic oxidation of the benzylic alcohol group in β-O-4 linked lignin model dimers to the corresponding carbonyl products using molecular oxygen under atmospheric pressure. The synergistic effect between Au NPs and the basic Li-Al LDH support induces further reaction of the oxidized model compounds, facilitating facile cleavage of the β-O-4 linkage. Extension to oxidation of γ-valerolactone (GVL) extracted lignin and kraft lignin using Au/Li-Al LDH under similar conditions produced a range of aromatic monomers in high yield. Hydrolysis of the Au/Li-Al LDH oxidized lignin was found to increase the degree of lignin depolymerization, with monomer yields reaching 40% for GVL extracted lignin. Based on these results, the Au/Li-Al LDH + O2 catalyst system shows potential to be an environmentally friendly means of depolymerizing lignin to low molecular weight aromatics under mild conditions